1. Field of the Invention
The subject matter of the present invention is ionic perfluorovinyl compounds, the polymers obtained from these compounds and their applications.
2. Description of the Prior Art
Polyelectrolytes of polyanion type incorporating functional groups of sulfonate or carboxylate type are known as ion-exchange resins (polyacrylic acid, polystyrenesulfonic acid optionally crosslinked with divinylbenzene). These polyelectrolytes are dissociated solely in the presence of water or of highly polar protic solvents, such as polyalcohols, for example ethylene glycol or glycerol. The corresponding acid groups (carboxylic or sulfonic acids) do not exhibit marked catalytic properties due to the absence of swelling of the resin and the strong association of ion pairs. In the form of membranes, these polymers only have a mediocre stability under the operating conditions of a hydrogen-air fuel cell; in particular, they are rapidly degraded by oxidizing species present on the oxygen electrode side. Likewise, these polymers cannot be used in membrane processes, such as the chlorine-sodium hydroxide electrochemical process.
Furthermore, perfluorinated membranes (Nafion(copyright)) carrying sulfonic groups are known which exhibit good chemical stability under the operating conditions of a fuel cell and for the chlorine-sodium hydroxide process. These materials are copolymers of tetrafluoroethylene (TFE) and of a comonomer carrying sulfonyl functional groups. However, the impossibility of crosslinking these polymers requires that the density of ionic groups be kept low, in order to prevent the resulting polymers from being excessively soluble or swollen by water, resulting in a mediocre mechanical strength and a relatively limited conductivity. Furthermore, these membranes exhibit a high permeability to gases (oxygen and hydrogen) and to certain solvents, such as methanol, which is harmful to the energy efficiency of fuel cells, more especially those of methanol-air type (xe2x80x9ccrossoverxe2x80x9d). Furthermore, although the sulfonate groups attached to perfluorinated groups are partially dissociated in aprotic solvents and although the solvating polymers are particularly advantageous for secondary batteries in which the reactions at the electrodes involve lithium ions, the conductivity of the gels obtained by swelling Nafion(copyright) membranes with aprotic solvents, alone or as a mixture, and the conductivity of the mixtures of these polyelectrolytes with polyethers based on ethylene oxide remain too low. Furthermore, the significant fraction of perfluorinated segments xe2x80x94CF2CF2xe2x80x94 resulting from the TFE comonomer makes these compounds sensitive to reduction at potentials close to those of the negative electrode, resulting in the polymer being destroyed. Moreover, the chemistry of these polymers is complex and expensive, and the yield in the manufacture of the monomer of perfluorovinyl ether type:
CF2xe2x95x90CFxe2x80x94Oxe2x80x94[CF2CF(CF3)]pxe2x80x94Oxe2x80x94CF2CF2SO2F, 0xe2x89xa6pxe2x89xa65
by thermal cracking of perfluoropolyethers-acid fluoride obtained by addition of CF3CFxe2x95x90CF2 to isomerized sultones is low and limits the use of these materials.
Polymers which comprise anions attached to the backbone of the polymer and which are optionally plasticized or gelled by a solvent of polar type are of great advantage in electrochemical systems, such as primary or secondary batteries, supercapacitors or systems for modulating light (electrochromic windows). Such polymers are mainly derivatives of ethylene oxide, of acrylonitrile, of polyesters of alkyl or oxaalkyl acrylate or methacrylate type, or of vinylidene fluoride. The production of monomers carrying highly delocalized anionic functional groups which can be incorporated, either by copolymerization or by cocrosslinking or alternatively by mixing polymers, in macromolecular materials such as those used in the electrochemical systems described above is therefore highly advantageous. The ionic monomers described above as components of membranes of Nafion(copyright) type cannot be suitable for this use because the high fraction of perfluorinated segments necessary in order to obtain the maximum conductivity in aprotic media (≈1M.1xe2x88x921) corresponds to a decreased dielectric constant in the vicinity of the ions and to an increased segmental stiffness, which are unfavorable to the movement of the ions. Moreover, the sulfonate groups are insufficiently dissociated in comparison with the salts of anions delocalized from nitrogenous centers or from carbon, such as, for example, the anion corresponding to the formula (RFSO2)X(SO2Rxe2x80x2F)xe2x88x92, in which X is N, Cxe2x80x94R or Cxe2x80x94SO2Rxe2x80x3F, RF, Rxe2x80x2F and Rxe2x80x3F are chosen from fluorine and fluorinated monovalent groups, or else RF and Rxe2x80x2F form the components of a divalent ring, and Rxe2x95x90H or any monovalent organic radical.
W. Navarrini et al. (U.S. Pat. No. 5,103,049) disclose methods for the preparation of Rfxe2x80x94CFxe2x95x90CFxe2x80x94SO2F compounds in which Rf is F or a perfluoroalkyl group comprising 1 to 9 carbon atoms. Among these compounds, only CF2xe2x95x90CFxe2x80x94SO2F is capable of acting as basis for monomers which can polymerize without steric constraints. However, this material has been shown to be too reactive to act as a precursor for monomer salts and anions, because the nucleophilic addition to the Cxe2x95x90C double bond, which is depleted in electrons both by the fluorine atoms and by the xe2x80x94SO2F group, generally takes place more rapidly than the substitution of the fluorine of the SO2F group, thus preventing access to ionic monomers or to precursors of ionic compounds (xe2x80x9cStudies of the Chemistry of Perfluorovinylsulfonyl Fluoridexe2x80x9d, Forohar Farhad, Clemson University, Thesis 1990 UMI 9115049). In particular, the methods for the preparation of anionic compounds used with RFSO2F compounds cannot be applied to the compound CF2xe2x95x90CFxe2x80x94SO2F. A process which consists in attaching a perfluorovinyl group to a phenyl nucleus carrying an SO2F group has been provided by C. Stone et al. (WO/96/39379); however, in this case too, it is not possible to convert the CF2xe2x95x90CFxe2x80x94C6H4SO2F molecule to an anionic monomer because of the sensitivity of the CF2xe2x95x90CFxe2x80x94 group, which is more reactive than xe2x80x94SO2F with respect to bases of OHxe2x88x92 or NH3 type.
Another process for the preparation of monomers of the TFE type comprising an anion has been provided by D. Desmarteau et al. (U.S. Pat. No. 5,463,005). It consists in preparing a compound comprising a perfluorovinyl group and an SO2F group, in protecting the perfluorovinyl group, for example by addition of Cl2, in converting the SO2F group to an ionic group and in then deprotecting the perfluorovinyl group. Such a process is nevertheless lengthy and expensive and the polymers obtained from said monomers exhibit the same disadvantages as the polymers of Nafion(copyright) type, resulting from the low content of SO3xe2x88x92 or sulfonimide ions in the absence of crosslinking.
The aim of the present invention is to provide a novel family of ionic compounds, which compounds exhibit extensive delocalization of the negative charge and good activity in polymerization or in copolymerization and allow the preparation of macromolecules possessing dissociated and stable ionic functional groups, and a process for the preparation of these compounds from fluorinated derivatives which are commercially available at low cost, for example hydrofluorocarbons or halocarbons.
For this reason, the subject matter of the present invention is ionic monomer compounds, the homopolymers and the copolymers obtained from these compounds, their applications and a process for their preparation.
A compound according to the invention is an ionic compound in which the negative charge is highly delocalized and which corresponds to the formula
[CF2xe2x95x90CFxe2x80x94Axe2x88x92]mMm+,
in which:
Mm+ is a proton or a metal cation having the valency m chosen from the ions of alkali metals, of alkaline earth metals, of transition metals or of rare earth metals or an organic onium cation or an organometallic cation, 1xe2x89xa6mxe2x89xa63;
Axe2x88x92 represents an anionic group corresponding to one of the following formulae:
[xe2x80x94(CF2)nxe2x80x94SO2Z]xe2x88x92xe2x80x83xe2x80x83(I)
[xe2x80x94(O)nxe2x80x2-"PHgr"-SO2Z]xe2x88x92xe2x80x83xe2x80x83(II)

n and nxe2x80x2 represent 0 or 1;
"PHgr" represents a condensed or noncondensed aromatic group, which may or may not carry one or more substituents and which may or may not comprise heteroatoms, or a polyhalogenated group xe2x80x94C6H(4-x-y)FxClyxe2x80x94 (1xe2x89xa6x+yxe2x89xa64);
Z represents xe2x80x94O or one of the xe2x80x94NCxe2x89xa1N, xe2x80x94C(Cxe2x89xa1N)2, xe2x80x94NSO2R or xe2x80x94C[SO2R]2 groups, Z being other than xe2x80x94O when n or nxe2x80x2 are zero;
D represents a single bond, an oxygen atom, a sulfur atom, a xe2x80x94COxe2x80x94 carbonyl group or an xe2x80x94SO2xe2x80x94 sulfonyl group;
the groups X1 to X4, hereinafter denoted by Xi, represent N, Cxe2x80x94Cxe2x89xa1N, CR, CCOR or CSO2R, it being understood that, in a pentacyclic group, the Xi groups can be identical or different;
R represents Y, YOxe2x80x94, YSxe2x80x94, Y2Nxe2x80x94, F, RFxe2x95x90CqF2q+1 (preferably 0xe2x89xa6qxe2x89xa612), CF2xe2x95x90CFxe2x80x94, CF2xe2x95x90CFCF2xe2x80x94 or CF2xe2x95x90CFxe2x80x94Oxe2x80x94, it being understood that, if 2 R substituents are present on the same group, they can be identical or different;
Y represents H or a monovalent organic radical having from 1 to 16 carbon atoms chosen from alkyl, alkenyl, oxaalkyl, oxaalkenyl, azaalkyl, azaalkenyl, aryl or alkylaryl radicals or from the radicals obtained from the abovementioned radicals by substitution, in the chains and/or the aromatic part, by heteroatoms, such as halogens, oxygen, nitrogen, sulfur or phosphorus, it being understood that, if sulfur or phosphorus are present, they can optionally be bonded to substituted nitrogen or oxygen atoms, or else Y is a repeat unit of a polymeric backbone.
The divalent radical "PHgr" can be a phenyl C6H4 corresponding to the ortho, meta and para positions of substitution. It can be an aromatic group, a phenyl which is substituted and/or comprising condensed nuclei which may or may not comprise heteroatoms. "PHgr" is preferably a halogenated phenyl group or a phenyl group carrying 1 to 2 CF3 substituents or a pyridyl nucleus.
When Mm+ is a metal cation, it can be an alkali metal (in particular K+ or Li+), an alkaline earth metal (in particular Mg++, Ca++ or Ba++), a transition metal (in particular Cu++, Zn++ or Fe++) or a rare earth metal (in particular Re+++).
When Mm+ is an onium cation, it can be chosen from ammonium ions [N(Yj)4]+, amidinium ions RC[N(Yj)2]2+, guanidinium ions C[N(Yj)2]3+, pyridinium ions [C5N(Yj)6]+, imidazolium ions C3N2(Yj)5+, imidazolinium ions C3N2(Yj)7+, triazolium ions C2N3(Yj)4+, carbonium ions C5(Yj)5C+, NO+ (nitrosyl) or NO2+ ions, sulfonium ions [S(Yj)3]+, phosphonium ions [P(Yj)4]+ and indonium ions [I(Yj)2]+. In the various abovementioned onium ions, the Yj substituents of the same cation can be identical or different. They represent one of the substituents indicated above for Y.
When Mm+ is an organometallic cation, it can be chosen from metalloceniums. It can also be chosen from metal cations coordinated by atoms, such as O, S, Se, N, P or As, carried by organic molecules, these cations optionally forming part of a polymeric backbone. Mm+ can also be a cation derived from the alkyl groups defined for Y above and limited to those having from 1 to 10 carbon atoms, for example a trialkylsilyl, trialkylgermanyl or trialkylstannyl derivative; in this case, M is connected to [CF2xe2x95x90CFxe2x80x94A] by a very labile covalent bond and the compound behaves as a salt. The Mm+ cation can also be the repeat unit of a conjugated polymer in cationic oxidized form.
Mention may be made, among the compounds of the present invention, of the following monofunctional monomers: {[CF2xe2x95x90CFxe2x80x94SO2NCN]xe2x88x92}mMm+, {[CF2xe2x95x90CFxe2x80x94SO2C(CN)2]xe2x88x92}mMm+, {[CF2xe2x95x90CFCF2xe2x80x94SO2NCN]xe2x88x92}mMm+, {[CF2xe2x95x90CFCF2xe2x80x94SO2C(CN)2]xe2x88x92}mMm+, {[CF2xe2x95x90CF-"PHgr"SO2NCN]xe2x88x92}mMm+, {[CF2xe2x95x90CF-"PHgr"SO2C(CN)2]xe2x88x92}mMm+, {[CF2xe2x95x90CF-"PHgr"SO2NSO2CF3]xe2x88x92}mMm+, {[CF2xe2x95x90CF-"PHgr"SO2C(SO2CF3)2]xe2x88x92}mMm+, {[CF2xe2x95x90CF-"PHgr"SO2CH(SO2CF3)]xe2x88x92}mMm+, 
Mention may also be made of the following di- and trifunctional monomers {[(CF2xe2x95x90CFCF2xe2x80x94SO2)2N]xe2x88x92}mMm+, {[(CF2xe2x95x90CFSO2)2CH]xe2x88x92}mMm+, {[(CF2xe2x95x90CFCF2xe2x80x94SO2)2CH]xe2x88x92}mMm+, {[(CF2xe2x95x90CFxe2x80x94SO2)3C]xe2x88x92}mMm+, {[(CF2xe2x95x90CFCF2xe2x80x94SO2)3C]xe2x88x92}mMm+, {[(CF2xe2x95x90CF-"PHgr"SO2)2N]xe2x88x92}mMm+, {[(CF2xe2x95x90CFxe2x80x94O-"PHgr"SO2)2N]xe2x88x92}mMm+, {[(CF2xe2x95x90CF-"PHgr"SO2)2CH]xe2x88x92}mMm+, {[(CF2xe2x95x90CFxe2x80x94O-"PHgr"SO2)2CH]xe2x88x92}mMm+, {[CF2xe2x95x90CF-"PHgr"SO2)3C]xe2x88x92}mMm+, {[(CF2xe2x95x90CFxe2x80x94O-"PHgr"SO2)2CH]xe2x88x92}mMm+, {[CF2xe2x95x90CF-"PHgr"SO2)3C]xe2x88x92}mMm+, {[(CF2xe2x95x90CFxe2x80x94O-"PHgr"SO2)3C]xe2x88x92}mMm+, {[CF2xe2x95x90CFxe2x80x94)2C6H3SO3]xe2x88x9256mMm+, {[3,5-(CF2xe2x95x90CFxe2x80x94)2C6H3SO2NSO2CF2]xe2x88x92}Mm+
Preference is very particularly given, among the above-mentioned compounds, to those in which "PHgr" is xe2x80x94C6H4xe2x80x94.
The ionic monomer compounds of the present invention can be prepared by various synthetic routes.
In a first embodiment, a compound comprising the perfluorovinyl group is reacted with an ionic compound having an anionic part A1, the structure of which is analogous to that of the anionic part A of the desired compound, and having from one to 3 leaving groups.
The subject matter of the invention is a process for the preparation of an ionic monomer compound [CF2xe2x95x90CFxe2x80x94Axe2x88x92]mMm+ as defined above in which an organometallic compound (OM1) is reacted in stoichiometric proportions with an ionic compound (IC1) in the presence of a catalyst, characterized in that:
the organometallic compound (OM1) corresponds to the formula [CF2xe2x95x90CFxe2x80x94(CF2)n]exe2x80x94E, in which:
E represents Li, MgL1, ZnL1, CdL1, Cu, Mg, Zn, Cd, Hg or a trialkylsilyl, trialkylgermanyl or trialkylstannyl group;
n is 0 or 1;
e represents the valency of E;
L1 represents a leaving group chosen from halogens, pseudohalogens, including sulfonates, radicals comprising imidazole or 1,2,4-triazole rings and their homologs in which one or more carbon atoms carry substituents, including those in which the substituents form a ring (for example a benzotriazole), perfluoroalkylsulfonyloxy radicals and arylsulfonyloxy radicals;
the ionic compound (IC1) corresponds to the formula [(LA1)xe2x88x92]mxe2x80x2Mxe2x80x2mxe2x80x2+ in which:
Mxe2x80x2mxe2x80x2+ represents a proton or a metal cation having the valency m chosen from ions of alkali metals, of alkaline earth metals, of transition metals or of rare earth metals, or an organic onium cation, or an organometallic cation, 1xe2x89xa6mxe2x89xa63. Mxe2x80x2 is chosen so as not to interfere with the formation reaction;
L has the same meaning as L1, it being understood that the L and L1 groups of the respective reactants used during a reaction can be identical or different;
A1 represents an anionic group corresponding to one of the following formulae:
[xe2x80x94(CF2)nxe2x80x94SO2Z1]xe2x88x92
[xe2x80x94(O)nxe2x80x2-"PHgr"SO2Z1]xe2x88x92

in which:
n and nxe2x80x2 represent 0 or 1;
D represents a single bond, an oxygen atom, a sulfur atom, a xe2x80x94COxe2x80x94 carbonyl group or an xe2x80x94SO2xe2x80x94 sulfonyl group;
Z1 represents the xe2x80x94O oxygen (except if n or nxe2x80x2 are zero) or one of the xe2x80x94NCxe2x89xa1N, xe2x80x94C(Cxe2x89xa1N)2, xe2x80x94NSO2R1 and xe2x80x94C[SO2R1]2 groups;
the Xxe2x80x21 to Xxe2x80x24 groups, hereinafter denoted by Xxe2x80x2i, represent N, Cxe2x80x94Cxe2x89xa1N, CR1, CCOR1 or CSO2R1, it being understood that, in a pentacyclic group, the Xxe2x80x2i groups can be identical or different;
R1 represents Y, YOxe2x80x94, YSxe2x80x94, Y2Nxe2x80x94, F, CF2xe2x95x90CFxe2x80x94, CF2xe2x95x90CFCF2xe2x80x94, CF2xe2x95x90CFxe2x80x94Oxe2x80x94 or RFxe2x95x90CqF2q+1 (0xe2x89xa6qxe2x89xa612), or a leaving group chosen from halogens, pseudohalogens, including sulfonates, radicals comprising imidazole or 1,2,4-triazole rings and their homologs, perfluoroalkylsulfonyloxy radicals and arylsulfonyloxy radicals, it being understood that, if two R1 substituents are present on the same group, they can be identical or different and that at most two R1 substituents are leaving groups;
Y has the meaning given above.
When the Mxe2x80x2 cation of the reactant used is different from the M cation of the desired final compound, the compound obtained is modified by conventional cation-exchange techniques.
The preferred leaving groups L and L1 are F, Cl, Br, I, the imidazole radical, the trifluoromethanesulfonyloxy radical CF3SO3xe2x80x94 and arylsulfonyloxy radicals.
Preference is very particularly given, for the ionic compounds (IC1), to the following anionic groups:
[(FSO2)NSO2RF]xe2x88x92, [(ClSO2)NSO2RF]xe2x88x92, [(ImSO2)NSO2RF]xe2x88x92, [(FSO2)2N]xe2x88x92, [(ClSO2)2N]xe2x88x92, [(ImSO2)2N]xe2x88x92, [(FSO2)NCN]xe2x88x92, [(ClSO2)NCN]xe2x88x92, [(ImSO2)NCN]xe2x88x92, [(FSO2)C(R)SO2RF]xe2x88x92[(ClSO2)C(R)SO2RF]xe2x88x92, [(ImSO2)C(R)SO2RF]xe2x88x92, [(FSO2)2CR]xe2x88x92, [(ClSO2)2CR]xe2x88x92, [(ImSO2)2CR]xe2x88x92, [(FSO2)C(CN)2]xe2x88x92, [(ClSO2)C(CN)2]xe2x88x92, [(ImSO2)C(CN)2]xe2x88x92, [(FSO2)3C]xe2x88x92, [(ClSO2)3C]xe2x88x92, [(ImSO2)3C]xe2x88x92, [(Cl"PHgr"SO2)NSO2RF]xe2x88x92, [(Br"PHgr"SO2)NSO2RF]xe2x88x92, [(I"PHgr"SO2)NSO2RF]xe2x88x92, [(CF3SO3"PHgr"SO2)NSO2RF]xe2x88x92, [(CH3"PHgr"SO3"PHgr"SO2)NSO2RF]xe2x88x92, [3,5-Br2C6H3SO3]xe2x88x92, [3,5-Br2C6H3SORF]xe2x88x92, [3,5-I2C6H3SO3]xe2x88x92, [3,5-I2C6H3SO2N(SO2RF)]xe2x88x92, [(Br"PHgr"SO2)NCN]xe2x88x92, [(I"PHgr"SO2)NCN]xe2x88x92, [(CF3SO3"PHgr"SO2)NCN]xe2x88x92, [(CH3"PHgr"SO3"PHgr"SO2)NCN]xe2x88x92, [(CH3"PHgr"SO2)C(CN)2]xe2x88x92, [(Br"PHgr"SO2)C(CN)2]xe2x88x92, [(I"PHgr"SO2)C(CN)2]xe2x88x92, [(CF3SO3"PHgr"SO2)C(CN)2]xe2x88x92, [(CH3"PHgr"SO3"PHgr"SO2)C(CN)2]xe2x88x92, [(Cl"PHgr"SO2)N(SO2"PHgr"Cl)]xe2x88x92, [(Br"PHgr"SO2)N(SO2"PHgr"Br)]xe2x88x92, [(I"PHgr"SO2)N(SO2"PHgr"I)]xe2x88x92, [(CF3SO3"PHgr"SO2)N(SO2"PHgr"SO3CF3)]xe2x88x92, [(CH3"PHgr"SO3"PHgr"SO2)N(SO2"PHgr"SO3"PHgr"CH3)]xe2x88x92, [(Cl"PHgr"SO2)2C(SO2RF)]xe2x88x92, [(Br"PHgr"SO2)2C(SO2RF)]xe2x88x92, [(I"PHgr"SO2)2C(SO2RF)]xe2x88x92, [(CF3SO3"PHgr"SO2)2C(SO2RF]xe2x88x92, [(Cl"PHgr"SO2)C(SO2RF)2]xe2x88x92, [(Br"PHgr"SO2)C(SO2RF)2]xe2x88x92, [(I"PHgr"SO2)C(SO2RF)2]xe2x88x92, [(CF3SO3"PHgr"SO2)C(SO2RF)2]xe2x88x92, [(CH3"PHgr"SO3"PHgr"SO2)C(SO2RF)2]xe2x88x92, [Br"PHgr"C(SO2RF)]xe2x88x92, [3,5-Br2C6H3C(SO2RF)2]xe2x88x92, 
In the abovementioned anionic groups of the compounds (IC1), R and RF have the meaning given above and preferably comprise from 0 to 10 carbon atoms.
A compound (OM1) such as CF2xe2x95x90CFxe2x80x94Li is prepared by reaction of a strong base B and of a lithiating agent Rxe2x80x2xe2x80x94Li with 1,1,1,2-tetrafluoroethane at low temperature, according to the reaction scheme:
CF3xe2x80x94CH2F+B= greater than CF2xe2x95x90CHF+[BHF]
CF2xe2x95x90CHF+Rxe2x80x2Li= greater than CF2xe2x95x90CFLi++Rxe2x80x2H
The compounds CF2xe2x95x90CFxe2x80x94E in which E is other than Li can be obtained by ion exchange.
It is advantageous to use butyllithium both as strong base and as lithiating agent.
The compound CF2xe2x95x90CFCF2xe2x80x94E can be prepared from perfluoroallyl fluorosulfate by simple nucleophilic substitution according to the following reaction scheme:
CF2xe2x95x90CFCF2xe2x80x94SO3F+M+Exe2x88x92= greater than CF2xe2x95x90CFCF2xe2x80x94E+M+SO3Fxe2x88x92
KI is a particularly appropriate compound M+Exe2x88x92.
The organometallic compounds (OM1) are more particularly chosen from: CF2xe2x95x90CFLi, (CF2xe2x95x90CF)2-xMg(Hal)x, (CF2xe2x95x90CF)2-xZn(Hal)x, (CF2xe2x95x90CR)2-xCd(Hal)x(0xe2x89xa6xxe2x89xa62); Hal=Cl, Br, I, pseudohalogen), (CF2xe2x95x90CF)3-yAl(Hal)y, (0xe2x89xa6yxe2x89xa63); CF2xe2x95x90CFCu, CF2xe2x95x90CFSi(CH3)3, CF2xe2x95x90CFSi(C2H5)3, CF2xe2x95x90CFSn(CH3)3, CF2xe2x95x90CFSn(C2H5)3, CF2xe2x95x90CFSn(C4H9)3, CF2xe2x95x90CFCF2CdBr, CF2xe2x95x90CFCF2Cu, CF2xe2x95x90CFCF2Zn(O3SF), CF2xe2x95x90CFCF2Si(CH3)3 and CF2xe2x95x90CFCF2Si(C2H5)3.
It is known to a person skilled in the art that the stability and the processing conditions for halogenated organometallic compounds vary according to the nature of E; in particular, organolithium compounds are only stable at temperatures of less than xe2x88x9260xc2x0 C. and are habitually prepared and used at the temperature of dry ice, whereas more covalent compounds, such as silane derivatives, are stable even above room temperature.
The process is carried out in the presence of a catalyst chosen from derivatives of nickel or palladium coordinated with bases of amine or phosphine type. Mention may be made, by way of example, of nickel bis(2,2xe2x80x2-bipyridyl), nickel tetrakis(triphenylphosphine) and its sulfonated derivatives, palladium acetate, trisbenzylideneketonedipalladium, palladium tetrakis(triphenylphosphine) and its sulfonated derivatives, and the compounds obtained by replacement of two triphenylphosphine molecules by [(C6H5)2PCH2]2 or [(C6H5)2PCH2]2CH2. Nickel and palladium have catalytic properties for so-called Suzuki coupling reactions when their degree of oxidation is greater than or equal to 0 and less than or equal to 2.
In another embodiment of the invention, an ionic monomer compound [CF2xe2x95x90CFxe2x80x94Axe2x88x92]mMm+ according to the invention is prepared by reacting a compound comprising a protected fluorovinyl group CF2L3CFL4xe2x80x94(CF2)nE1 with a reactant [(L5)aA2]mxe2x80x2Mxe2x80x2mxe2x80x2+ making possible the formation of the anionic group A and then the protective groups are removed by a chemical or electrochemical reduction or by a dehydrohalogenation. Mxe2x80x2 has the meaning indicated above. L3 and L4 represent H or a halogen, just one among them optionally being H. E1 has the meaning given above for E. L5 represents a leaving group having the same definition as the leaving group L. xe2x80x9caxe2x80x9d is the valency of the anionic group A2. A2 represents a group corresponding to one of the following formulae [xe2x80x94(CF2)nxe2x80x94SO2Z2]xe2x88x92, [xe2x80x94(O)nxe2x80x2-"PHgr"SO2Z2]xe2x88x92 or 
in which:
n, nxe2x80x2, D and "PHgr" have the meaning indicated above;
Z2 represents the xe2x80x94O oxygen (except if n or nxe2x80x2 are zero) or one of the groups xe2x80x94NCxe2x89xa1N, xe2x80x94C(Cxe2x89xa1N)2, xe2x80x94NSO2R2 or xe2x80x94C[SO2R2]2;
the groups Xxe2x80x31 to Xxe2x80x34, hereinafter denoted by Xxe2x80x3i, represent N, Cxe2x80x94Cxe2x89xa1N, CR2, CCOR2 or CSO2R2, it being understood that, in a pentacyclic group, the Xxe2x80x3i groups can be identical or different;
R2 represents xe2x80x94OH, xe2x80x94SH, Y, YOxe2x80x94, YSxe2x80x94, Y2Nxe2x80x94, F, CF2xe2x95x90CFxe2x80x94, CF2xe2x95x90CFCF2xe2x80x94CFxe2x95x90CFxe2x80x94Oxe2x80x94 or RFxe2x95x90CqF2q+1 (0xe2x89xa6qxe2x89xa612), it being understood that, if two R2 substituents are present on the same group, they can be identical or different and that at most two R2 substituents represent xe2x80x94OH or xe2x80x94SH;
Y has the meaning given above.
Mention may be made, by way of example, of the following reaction:
(ClSO2)2NK+2CF2Clxe2x80x94CFClLi= greater than (CF2Clxe2x80x94CFClSO2)2NK+2LiCl.
When the cation Mxe2x80x2 of the reactant used is different from the cation M of the desired final compound, the compound obtained is modified by conventional cation-exchange techniques. The greater resistance of the compounds thus protected with respect to nucleophiles, in particular bases, makes it possible to carry out reactions on molecules acting as intermediate in the preparation of the monomer anions, reactions which would be impossible if the ethylenic double bond was unprotected. In particular, it is possible to form intermediates of sulfamide or hydrazide type allowing the construction of anionic species.
For example, the anion derived by addition of chlorine to trifluoroacrylic acid can be converted to a triazole group via a hydrazide. The triazole anion, more dissociated than the carboxyl anion, is obtained according to the simplified scheme: 
The starting fluorinated acrylic acid is easily prepared by reaction of CO2 with an organometallic derivative, such as CF2xe2x95x90CFLi, itself easily obtained by reaction of an alkyllithium with the commercial compound 1,1,1,2-tetrafluoroethane sold under the tradename Klea(copyright).
Similar reactions are possible with a compound comprising a sulfur-based anionic group, such as a sulfonate. They make it possible to obtain, via a sulfamide, a compound comprising an anionic sulfonylimide group which is more dissociated than the sulfonate group, by the following reaction stages:
sulfonate+chlorinating agent= greater than RSO2Cl
RSO2Cl+NH3= greater than RSO2NH2;
RSO2NH2+Rxe2x80x2SO2Cl= greater than RSO2N(H)SO2Rxe2x80x2
These reactions cannot be carried out if Rxe2x95x90CF2xe2x95x90CF. On the other hand, the desired result is obtained if Rxe2x95x90CF2Clxe2x80x94CFCl and, for example, Rxe2x80x2xe2x95x90R or CF3. The sulfonate is easily obtained by the following reactions:
CF2Clxe2x80x94CFClLi+ClSO3Si(CH3)3= greater than CF2Clxe2x80x94CFSO3Li+ClSi(CH3)3.
A compound [CF2L2xe2x80x94CFL3xe2x80x94(CF2)n]xe2x80x94E1, in particular CF2ClCFClLi, can be obtained by reaction of the corresponding compound [CF2xe2x95x90CFxe2x80x94(CF2)n]xe2x80x94E1 with a compound L2L3 at a temperature of between xe2x88x9280xc2x0 C. and 110xc2x0 C., for example in the Trapp mixture (THF/ether/pentane composition). Mention may be made, among the compounds L2L3 which are easily added to the perfluorovinyl double bond, of FCl, Cl2, ClBr, Br2, ICl, IBr, I2, (SCN)2, HCl, HBr and HI. The lithium compounds (OM2) can act as the basis for the preparation of other organometallic compounds, such as silicon or zinc derivatives, by exchange.
The (L2)/(L3) and L2H pairs are preferably chosen from Cl2, Br2, FCl, FBr, BrCl, ICl, HF, HCl and HBr, Cl2 and HCl being particularly preferred.
The L2L3 groups are easily removed by reduction or by dehydrohalogenation. The reducing agent is advantageously chosen from zinc, the copper-zinc couple, Ti3+, V2+, Cr3+ or Sm2+ salts, and tetrakis(dimethylaminoethylene) {[(CH3)2N]2Cxe2x95x90}2. An electrochemical reduction can also be carried out, directly or via the preceding metals acting as mediators. The dehydrohalogenating agents are chosen from strong bases and are known to a person skilled in the art. Mention may in particular be made of NaH [optionally used in the presence of phosphorus-comprising bases of phosphazene P1-P4 type (Fluka AG, Basle, Catalog No. 79408, 79412, 79417, 79421, 422 79432)], (CH3)3CONa, (CH3)3COK, LDA (lithium diisopropylamide), [(CH3)2CH]2NLi, or hexaalkyldisilazane derivatives, in particular [(CH3)3Si]2NLi, [(CH3)3Si]2NNa and [(CH3)3Si]2NK.
In another embodiment, an ionic compound having an anionic part A3, the structure of which is analogous to that of the anionic part A of the desired compound, and having from one to 3 hydroxyl or thiol groups is reacted with a compound comprising the perfluorovinyl group.
The subject matter of the invention is a process for the preparation of an ionic monomer compound [CF2xe2x95x90CFxe2x80x94Axe2x88x92]mMm+ as defined above, characterized in that a compound CF2xe2x95x90CFL2, in which L2 represents Cl, Br or F, is reacted in stoichiometric proportions with an ionic compound (IC2) [(HQA3)xe2x88x92]mxe2x80x2(Mxe2x80x2)mxe2x80x2+ and in that the addition product obtained is treated with a strong base B.
The reaction scheme is as follows:
CF2xe2x95x90CFL2+(HQA3)xe2x88x92= greater than HCF2xe2x80x94CFL2xe2x80x94Qxe2x80x94A3
HCF2xe2x80x94CFL2xe2x80x94Qxe2x80x94A3+Base= greater than CF2xe2x95x90CFxe2x80x94Qxe2x80x94A3+BaseHL
The cationic part (Mxe2x80x2)mxe2x80x2+ has the meaning given above, alkali metal cations being preferred.
The anionic part (HQA3)xe2x88x92 is such that:
Q represents O or S;
A3 represents an anionic group corresponding to one of the following formulae:
[xe2x80x94(CF2)nxe2x80x94SO2Z3]xe2x88x92
[-"PHgr"SO2Z3]xe2x88x92

in which:
n and "PHgr" have the meaning indicated above;
Z3 represents the xe2x80x94O oxygen (except if n is zero) or one of the groups xe2x80x94NCxe2x89xa1N, xe2x80x94C(Cxe2x89xa1N)2, xe2x80x94NSO2R3 or xe2x80x94C[SO2R3]2;
the groups Xxe2x80x3xe2x80x21 to Xxe2x80x3xe2x80x24, hereinafter denoted by Xxe2x80x3xe2x80x2i, represent N, Cxe2x80x94Cxe2x89xa1N, CR3, CCOR3 or CSO2R3, it being understood that, in a pentacyclic group, the Xxe2x80x3xe2x80x2i groups can be identical or different;
R3 represents HOxe2x80x94, HSxe2x80x94, Y, YOxe2x80x94, YSxe2x80x94, Y2Nxe2x80x94, F, CF2xe2x95x90CFxe2x80x94, CF2xe2x95x90CFCF2xe2x80x94, CF2xe2x95x90CFxe2x80x94Oxe2x80x94 or RFxe2x95x90CqF2q+1 (0xe2x89xa6qxe2x89xa612), it being understood that, if two R3 substituents are present on the same group, they can be identical or different and that at most two R3 substituents are xe2x80x94OH or xe2x80x94SH groups;
Y is as defined above.
The strong base B can be in particular NaH [optionally used in the presence of phosphorus-comprising bases of phosphazene P1-P4 type (Fluka AG, Basle, Catalog No. 79408, 79412, 79417, 79421, 422 79432)], (CH3)3CONa, (CH3)3COK, LDA (lithium diisopropylamide), [(CH3)2CH]2NLi, or hexaalkyldisilazane derivatives, in particular [(CH3)3Si]2NLi, [(CH3)3Si]2NNa and [(CH3)3Si]2NK. Potassium t-butoxide is particularly appropriate.
When the ionic compound (IC2) comprises a thiol, it is possible to convert the sulfide of the anion [HCF2xe2x80x94CFL2SA]xe2x88x92 of the intermediate product obtained to the sulfone by oxidation. The electro-withdrawing power of the sulfone contributes to decreasing the basicity of the corresponding anion [HCF2xe2x80x94CFL2xe2x80x94SO2-A]xe2x88x92 and it is then possible to remove L2H under mild conditions, for example in the presence of a tertiary nitrogenous base.
The preferred compounds (IC2) are those which comprise one of the following anions: [{HO-("PHgr")SO2}N(SO2RF)]xe2x88x92, [{HS-("PHgr")SO2}N(SO2RF)]xe2x88x92, [{HO-("PHgr")SO2}NCN]xe2x88x92, [{HS("PHgr")SO2}NCN]xe2x88x92, [{HO("PHgr")SO2}C(CN)2]xe2x88x92, [{HS("PHgr")SO2}C(CN)2]xe2x88x92, [{HO("PHgr")SO2}N{SO2("PHgr")OH}]xe2x88x92, [{HS("PHgr")SO2}N("PHgr")SH]xe2x88x92, [{HO("PHgr")SO2}2C(R)]xe2x88x92, [{HO("PHgr")SO2}2C(SO2R)]xe2x88x92, [{HO("PHgr")SO2}2C(SO2RF)]xe2x88x92, [{HO("PHgr")SO2}C(SO2RF)2]xe2x88x92, [{HS("PHgr")SO2}2C(R)]xe2x88x92, [{HS("PHgr")SO2}2C(SO2R)]xe2x88x92, [{HS("PHgr")SO2}2C(SO2RF)]xe2x88x92, [{HS("PHgr")SO2}C(SO2RF)2]xe2x88x92, [3,5-(HO)2xe2x80x94C6H3SO3]xe2x88x92, [(3,5-(HO)2xe2x80x94C6H3SO2)N(SO2RF)]xe2x88x92, [3,5-(HO)2xe2x80x94C6H3C(SO2RF)]xe2x88x92, [{HO-("PHgr")SO2}2C(SO2RF)]xe2x88x92, [{HS-("PHgr")SO2}2C(SO2RF)]xe2x88x92, 
In another embodiment, the compounds [CF2xe2x95x90CFxe2x80x94Axe2x88x92]mMm+ are prepared by a process, characterized in that it consists in reacting a compound L6CF2CF2L6 with an ionic compound [(HQA3)xe2x88x92]mxe2x80x2(Mxe2x80x2)mxe2x80x2+ in stoichiometric proportions and in reducing the substitution compound obtained, either chemically or electrochemically. The compound [(HQA3)xe2x88x92]mxe2x80x2(Mxe2x80x2)mxe2x80x2+ is as defined above. L6 represents a leaving group chosen from halogens, pseudohalogens and sulfonates. Halogens are particularly preferred.
The substitution compounds obtained are subjected to a chemical reduction or an electrochemical reduction in order to remove the L6 leaving groups. The reduction can be catalyzed by zinc, the copper-zinc couple, Ti3+, V2+, Cr3+ or Sm2+ salts, and tetrakis(dimethylaminoethylene) {[(CH3)2N]2Cxe2x95x90}2. An electrochemical reduction can be carried out, directly or via the preceding metals acting as mediators.
The ionic compounds of the present invention, all of which comprise at least one CF2xe2x95x90CFxe2x80x94 group, can be polymerized by the radical route. The polymerization can be carried out in solution or in emulsion with conventional radical initiators, such as peroxides, azo compounds, persulfates, photoinitiators of benzoin type or others. During the preparation of crosslinked materials, the molecular mass between network nodes is not necessarily very high, which constitutes a significant advantage with respect to materials of the Nafion(copyright) type.
A polymer according to the present invention is composed of a polyanionic part with which are associated cations in a number sufficient to ensure the electronic neutrality of the polymer, the polyanionic part being composed of repeat units: 
in which A has the meaning given above in the definition of the monomer compounds of the present invention.
A polymer of the invention can also be composed of repeat units 
Such a polymer is obtained by polymerization of a difunctional compound according to the invention in which the anionic group Axe2x88x92 itself comprises a perfluorovinyl radical. 
Such a compound [(CF2xe2x95x90CF)2xe2x80x94Axe2x80x2xe2x88x92]mMm+ in which M has the meaning given above and Axe2x80x2 represents an anion corresponding to one of the formulae (I), (II) or (III) mentioned above in which a Z or Xi substituent comprises a perfluorovinyl radical. In this case, two perfluorovinyl radicals form a ring comprising 4 carbons which is connected to an analogous ring via the anionic part Axe2x80x2 in order to form a linear polymer.
The polymerization can be carried out starting from only the compounds of the invention and a homopolymer is obtained in which each of the repeat units carries an ionic group.
When the polymerization is carried out in the presence of a comonomer, it is possible to limit the amount of ionic groups on the copolymer.
The polymerization of monofunctional monomers makes it possible to obtain linear polymers. The polymerization of di- or trifunctional monomers, in which the anionic group A itself comprises one or two additional CF2xe2x95x90CFxe2x80x94 groups, makes it possible to obtain crosslinked macromolecular materials. In this case also, a copolymerization with a comonomer not carrying ionic groups makes it possible to adjust the number of functional groups introduced.
Generally, when the compounds of the present invention are polymerized in the presence of a comonomer, the choice of the monomer, of the comonomer and of the number of polymerizable groups on the monomer and the comonomer makes it possible to adjust the properties of the macromolecular materials obtained according to the use which is anticipated for them.
The ionic compounds of the present invention comprise at least one ionophoric group. They can thus be used for the preparation of ion conducting materials. The polymers obtained from the monomer compounds of the invention, which have the property of polymerizing or of copolymerizing, comprise repeat units carrying an ionophoric group and can thus also be used for the preparation of ion conducting materials, with the advantage of having an immobile anionic charge. An ion conducting material constituted by an ionic monomer compound in solution in a solvent and an ion conducting material comprising a polymer obtained by polymerization of a monomer compound of the present invention consequently constitute further subject matters of the present invention.
The ion conducting materials of the present invention can be used for the preparation of the electrolyte or as binder of the electrodes of energy storage systems, such as primary or secondary batteries, fuel cells, in supercapacitors, in systems for modulating light transmission (electrochromic systems, electroluminescent diodes) or in sensors. An electrolyte obtained from a compound according to the invention can be a liquid electrolyte, a solid electrolyte or a gel electrolyte.
A plasticized electrolyte or an electrolyte in the gel form according to the invention can be composed of a mixture of at least one polar solvent, of an ionic monomer compound of the invention and of a polar polymer. It can also be composed of at least one polar solvent and a polymer or copolymer obtained by polymerization of a monofunctional compound according to the present invention.
A solid electrolyte according to the invention comprises either a copolymer of at least one compound according to the invention and of one or more precursors of solvating polyethers or a macromolecular material obtained by co-crosslinking of at least one compound according to the invention and of a solvating polyether carrying reactive functional groups capable of reacting with the perfluorovinyl group of the compounds of the invention. In another embodiment, a solid electrolyte can comprise a mixture of a polyether and of a homopolymer or of a copolymer obtained from at least one compound of the invention carrying ionic groups, it being possible for said mixture optionally to be crosslinked in order to form an interpenetrating network. In some cases, it can be advantageous to plasticize the macromolecular material by addition of a polar solvent which is compatible with the ether functional groups. Depending on the amount of polar solvent added, the electrolyte will be a plasticized solid electrolyte or a gel electrolyte. The polar solvent is chosen, for example, from linear ethers and cyclic ethers, esters, nitrites, nitro derivatives, amides, sulfones, alkylsulfamides and partially halogenated hydrocarbons.
An electrolyte can also be composed of a mixture of a homopolymer or of a copolymer of polar monomers (including a polyether) and of a homopolymer or of a copolymer of ionic compounds of the present invention. The two mixed polymers can optionally be crosslinked to form an interpenetrating network and be plasticized by a polar liquid.
An electrolyte generally comprises a solvent (liquid, solid or gel) and at least one salt. When, in accordance with the present invention, an electrolyte comprises a macromolecular material obtained from the compounds of the invention, the repeat units comprise ionic groups which can completely or partially replace the salt conventionally added to a polymer solvent in order to constitute a polymer electrolyte. Polymers derived from trifluorovinylsulfonyl(trifluoromethylsulfonyl)imide and those derived from trifluorovinylphenylsulfonyl(trifluoromethylsulfonyl)imide are particularly advantageous for the preparation of electrolytes. An electrolyte obtained from a polymer according to the invention, in which the anions are at least partly immobilized on a polymer chain, has a mainly cationic mobility, the effect of which is to greatly improve the operation of electrochemical systems. In addition, a compound of the invention can be used as salt added to a liquid or polymer electrolyte.
Use is preferably made, for the preparation of macromolecular materials of use as electrolyte, of compounds according to the invention in which the cation is an alkali metal cation. Lithium and potassium are particularly preferred. The more suitable anions are the mono- or difunctional imides
CF2xe2x95x90CFSO2NSO2CF3xe2x88x92 or [CF2xe2x95x90CFSO2]2Nxe2x88x92 or CF2xe2x95x90CFC6H4SO2CF3xe2x88x92.
When an electrolyte according to the present invention is used in an energy storage system, such as a primary battery or a secondary battery, it is advantageous to use, as negative electrode, an electrode composed of metallic lithium or one of its alloys, optionally in the form of a nanometric dispersion in lithium oxide, or double nitrides of lithium and of a transition metal, or oxides of low potential having the general formula Li4-x+yTi5+xO12 (0xe2x89xa6xxe2x89xa61, 0xe2x89xa6yxe2x89xa63), or carbon and carbonaceous products resulting from the pyrolysis of organic materials. The positive electrode will advantageously be chosen from vanadium oxides VOx (2xe2x89xa6xxe2x89xa62.5), LiV3O8 or LiyN1-xCoxO2 (0xe2x89xa6xxe2x89xa61; 0xe2x89xa6yxe2x89xa61), manganese spinels LiyMn1-xMxO2 (Mxe2x95x90Cr, Al, V, Ni, 0xe2x89xa6xxe2x89xa60.5; 0xe2x89xa6yxe2x89xa62), organic polydisulfides, FeS, FeS2, iron sulfate Fe2(SO4)3, iron and lithium phosphates and iron and lithium phosphosilicates with an olivine structure or analogous phosphosilicates in which the iron is replaced by manganese, and sulfophosphates with a Nasicon structure LixFe2S1-xPxO4. The above-mentioned compounds may be used alone or as a mixture.
When an electrolyte according to the present invention is used in a system for modulating light, such as an electrochromic system, use is preferably made of an electrode material chosen from WO3, MoO3, iridium oxyhydroxide IrOxHy, 2xe2x89xa6xxe2x89xa63; 0xe2x89xa6yxe2x89xa63), Prussian blue, viologen compounds and their polymers, and aromatic polyimides.
When an ionically conducting material of the present invention is used as electrolyte in an energy storage system, such as a supercapacitor, use is preferably made of an electrode material comprising a carbon with a high specific surface or an electrode comprising a redox polymer.
The monomer compounds of the present invention can be used for the doping of polymers for the purpose of conferring an improved electronic conduction on them. The polymers concerned are essentially polyacetylenes, polyphenylenes, polypyrroles, polythiophenes, polyanilines, polyquinolines, which may or may not be substituted, and polymers in which the aromatic units are separated by the vinylene unit xe2x80x94CHxe2x95x90CHxe2x80x94. The doping process consists in partially oxidizing the polymer in order to create carbocations, the charge of which is compensated for by the anions of the compounds of the invention. This doping can be carried out chemically or electrochemically, optionally simultaneously with the formation of the polymer. For this specific application, the choice is preferably made of the compounds of the invention carrying a highly delocalized charge, in particular compounds in which Z is xe2x80x94C(Cxe2x89xa1N)2, xe2x80x94NSO2R or xe2x80x94C(SO2R)2, which confer thermal and mechanical stability properties.
The compounds of the present invention can also be used to confer antistatic properties or microwave-absorbing properties on various materials. The materials concerned are, for example, polymers which take part in the composition of electronic components, textiles and windows. Homo- or copolymers of the compounds of the invention, which are preferably non-crosslinked in order to be able to be coated onto the surface on which the antistatic properties have to be induced, are compounds suited to this specific use. The comonomer of this type of application makes possible, if appropriate, a good adhesion to the substrate to be treated, by the choice of comparable polarities. In plastics, it is also possible to prepare mixtures with the polymer of the invention by techniques known in plastics technology.
A copolymer obtained by copolymerization of a mixture of monofunctional compounds and of difunctional compounds according to the present invention is of use in the preparation of membranes. The homopolymerization or the copolymerization of the monomers according to the invention having a perfluorovinyl functional group results in linear polymers. It is easy, by addition of monomers having more than one polymerizable functional group, to obtain crosslinked networks. These materials can be used for preparing membranes having an improved mechanical strength in which the degrees of swelling and the permeation in liquids in which they will be employed can be controlled. The improvement in the mechanical strength is also a significant factor in the preparation of very fine membranes in which the resistance is decreased and in the reduction of the cost of the starting materials. Likewise, controlling the degree of crosslinking makes it possible to increase the concentration of attached ions in the membrane without inducing excessive solubility or excessive swelling. In processes employing membranes, it is particularly advantageous to prepare the membrane in its definitive form, in the sheet or pipe form, from a concentrated solution of monomers in a solvent allowing spreading or extrusion techniques, by copolymerization of the monomers, including those which make possible the crosslinking.
In the preparation of membranes, it is particularly advantageous to use monomer compounds of the present invention which exhibit a high solubility in the solvents in which the polymerization will be carried out and a reactivity comparable with that of the double bonds carried by the monofunctional monomer and of those carried by the polyfunctional monomers which make possible the crosslinking, so as to obtain an even distribution of the crosslinking nodes.
The membranes obtained from the compounds of the present invention can be used in particular in dialysis systems, as separator in a two-phase reactor or for membrane processes of chlorine-sodium hydroxide type, or for the recovery of effluents, or as electrolyte in a fuel cell. As regards fuel cells, a macromolecular material obtained from monomer compounds of the invention can also be used as binder in the electrode material.
The monomer compounds of the present invention can be used for the catalysis of various types of chemical reactions and in particular for polymerization reactions, condensation reactions, addition or elimination reactions, oxidation or reduction reactions, solvolyses, Friedel-Crafts reactions and Diels-Alder reactions. For these applications in catalysis, the monomer compounds will be chosen essentially according to the cation associated with the anionic part. For the catalysis of Diels-Alder reactions or of Friedel-Crafts reactions, alkali metal, alkaline earth metal, transition metal or rare earth metal cations are preferred. It is also possible to use, for the abovementioned catalytic reactions, polymers obtained from the abovementioned monomer compounds. Polyanionic polymers comprising H+, Li+, Mg++, Ca++, Cu++, Zn++, Al+++ or Fe+++ cations or rare earth metal cations are preferred. Said polymers are generally put into the powder or granule form. In this case, the separation of the reactants becomes particularly easy due to the insolubility of the polyanion of the invention.
The compounds of the invention in which the cation is an onium of the diazonium, sulfonium, iodonium or metallocenium type can be used as cationic polymerization initiator. Under the action of actinic radiation, such compounds generate the corresponding acid form capable of initiating a cationic polymerization reaction. It is also possible to use polymers obtained by polymerization of the abovementioned monomer compounds. The advantages related to the use of polymers are analogous to those of the polymers used in the other abovementioned catalytic reactions. The materials of the invention in the amine salt form can be used as initiator of cationic polymerizations by heating, releasing the corresponding protonic form. Likewise, if the cation is a salt of a cationic azo compound (for example as represented below), it can act, by heating, as initiator of radical polymerizations. 
The present invention is described in more detail by the following examples, the invention not being restricted to these examples.